US7550515B2 - Process for the running of a reactor suitable for heterogeneous reactions combined with reactions taking place in three-phase systems - Google Patents

Process for the running of a reactor suitable for heterogeneous reactions combined with reactions taking place in three-phase systems Download PDF

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US7550515B2
US7550515B2 US10/572,516 US57251604A US7550515B2 US 7550515 B2 US7550515 B2 US 7550515B2 US 57251604 A US57251604 A US 57251604A US 7550515 B2 US7550515 B2 US 7550515B2
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vessel
reactor
catalyst
pressure
process according
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US20070135527A1 (en
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Cristina Maretto
Giovanni Pederzani
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IFP Energies Nouvelles IFPEN
Eni Tecnologie SpA
Eni SpA
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IFP Energies Nouvelles IFPEN
Eni Tecnologie SpA
Eni SpA
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
    • C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
    • C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
    • C10G2/34—Apparatus, reactors
    • C10G2/342—Apparatus, reactors with moving solid catalysts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
    • C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
    • C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
    • C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
    • C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
    • C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
    • C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
    • C10G2/334—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing molecular sieve catalysts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/40—Characteristics of the process deviating from typical ways of processing
    • C10G2300/4031—Start up or shut down operations

Definitions

  • the present invention relates to a process for the running of a reactor suitable for heterogeneous reactions combined with reactions taking place in three-phase systems.
  • the present invention relates to a process for the running of a reactor in which reactions take place in multiphase systems, wherein a gaseous phase, prevalently consisting of CO and H 2 , is bubbled into a suspension of a solid in the form of particles (catalyst) in a liquid (prevalently reaction product), according to the Fischer-Tropsch technology.
  • a gaseous phase prevalently consisting of CO and H 2
  • a liquid prevalently reaction product
  • Fischer-Tropsch technology is known in literature, for preparing hydrocarbons from mixtures of gas based on hydrogen and carbon monoxide, conventionally known as synthesis gas.
  • a document which summarizes the main works on the Fischer-Tropsch synthesis reaction is represented by Sie and Krishna, Appl. Catalysis A: General (1999), 186, 55-70.
  • the Fischer-Tropsch technology is typically based on the use of slurry reactors, reactors which are normally used in relation to chemical reactions which are carried out in multiphase systems in which a gaseous phase is bubbled into a suspension of a solid in a liquid.
  • the gaseous phase consists of synthesis gas, with a molar ratio H 2 /CO ranging from 1 to 3
  • the liquid phase, at the reaction temperature prevalently consists of the reaction product, i.e. essentially linear hydrocarbons with a high number of carbon atoms, and the solid phase is prevalently represented by the catalyst.
  • the Fischer-Tropsch reaction is an exothermic reaction which, for its industrial embodiment, requires internal heat exchanger devices, for removing the heat produced and for controlling the thermal profile inside the reactor.
  • the objective of the present invention is the running of the phases which are not included in the normal operating conditions for Fischer-Tropsch reactions and which are particularly critical for the catalyst performances, such as for example:
  • the charging phase of a catalyst into a bubble column slurry reactor (B) at the moment of start-up comprises:
  • the inert gas can consist, for example, of nitrogen or, preferably, purified natural gas.
  • the catalyst is englobed in paraffinic waxes in the form of cylindrical blocks, wherein the quantity of wax ranges from 30 to 70% by weight.
  • Any catalyst capable of being active in Fischer-Tropsch reactions can be used in the present process.
  • the preferred catalyst is based on Co dispersed on a solid carrier consisting of at least one oxide selected from one or more of the following elements: Si, Ti, Al, Zr, Mg.
  • Preferred carriers are silica, alumina or titania and their mixtures.
  • the cobalt is present in the catalyst in quantities ranging from 1 to 50% by weight, generally from 5 to 35% with respect to the total weight.
  • the catalyst can comprise further additional elements. It can comprise, for example, with respect to the total, from 0.05 to 5% by weight, preferably from 0.1 to 3%, of ruthenium and from 0.05 to 5% by weight, preferably from 0.1 to 3%, of at least a third element selected from those belonging to group 3 (IUPAC regulation). Catalysts of this type are known in literature and described, together with their preparation, in European patent 756,895.
  • catalysts are again based on cobalt but containing tantalum, as promoter element, in quantities of 0.05-5% by weight, with respect to the total, preferably 0.1-3%.
  • These catalysts are prepared by first depositing a cobalt salt on the inert carrier (silica or alumina), for example by means of the dry impregnation technique, followed by a calcination step and, optionally, a reduction and passivation step of the calcined product.
  • a derivative of tantalum is deposited on the catalytic precursor thus obtained, preferably with the wet impregnation technique followed by calcination and, optionally, reduction and passivation.
  • the catalyst whatever its chemical composition may be, is used in the form of a finely subdivided powder having an average diameter of the granules ranging from 10 to 250 ⁇ m.
  • the catalyst, englobed in the paraffinic matrix is brought to a temperature higher than or equal to 150° C., for example, from 150 to 220° C., and diluted with a diluent liquid at those temperatures, and also at room temperature, for example with an oligomer of C 6 -C 10 ⁇ -olefins, until a concentration of solid ranging from 10 to 50% by weight is obtained.
  • the suspension is transferred into the reactor (B), maintained at a temperature higher than or equal to that of the melting vessel (A), by means of an internal heat exchanger. Under normal operating conditions, the exchanger serves for removing the reaction heat produced and maintaining the conditions more or less isothermal in the whole reaction volume.
  • the reactor (B) is at a pressure lower than that present in the charging vessel (A) in order to favour the passage of the suspension from the vessel to the reactor due to the difference in pressure.
  • the pressure in the charging vessel (A) is generally higher than that present in the reactor (B) by about 0.2-0.4 MPa whereas the pressure inside the reactor is maintained at about 0.1-1 MPa.
  • a stream of inert gas ( 5 ) is maintained at the bottom of the reactor (B) to guarantee the suspension of the catalyst, thus preventing its sedimentation.
  • Both the temperature and pressure present inside the reactor (B) during the charging phase are lower than the values present during regime synthesis conditions.
  • the Fischer-Tropsch reaction is in fact carried out at temperatures equal to or higher than 150° C., for example ranging from 200 to 350° C., maintaining a pressure ranging from 0.5 to 5 MPa inside the reactor. More significant details on Fischer-Tropsch reactions are available in “Catalysis Science and Technology”, vol. 1, Springer-Verlag, New York, 1981.
  • the melting, dilution and transfer from the charging vessel (A) to the reactor (B) are repeated various times. In relation to the concentration of the catalyst desired and plant production capacity, this operation can be repeated, for example, from 2 to 30 times.
  • the reactor (B) is kept isolated from the optional equipment (E) envisaged for the treatment of the suspension, until an adequate suspension level is reached in the reactor itself enabling it to be on-line with said equipment (E).
  • the charging steps are then completed until the normal operating level is reached.
  • the vessels (A) and (B) have outlets ( 13 ) for the recovery of the vapour phase (inert gas and/or non-reacted synthesis gas, and/or synthesis reaction products in vapour phase under the reaction conditions).
  • a conditioning phase of the catalyst is activated. More specifically, at the end of the charging, the reactor (B) is in temperature conditions ranging from 150 to 220° C. and a pressure ranging from 0.1 to 1 MPa, and is continuously fed with inert gas.
  • the conditioning phase of the catalyst comprises:
  • Synthesis gas essentially consists of CO and H 2 , possibly mixed with CH 4 , CO 2 and inert gases in general; it has a H 2 /CO molar ratio ranging from 1 to 3 and preferably derives from steam reforming and/or partial oxidation of natural gas or other hydrocarbons, on the basis of the reactions described, for example, in U.S. Pat. No. 5,645,613.
  • the synthesis gas can derive from other productions techniques such as, for example, autothermal reforming, C.P.O. (Catalytic Partial Oxidation) or from the gasification of coal with water vapour at a high temperature as described in “Catalysis Science and Technology”, vol. 1, Springer-Verlag, New York, 1981.
  • the vessels (C) and (D) have outlets ( 13 ′) for recovering the vapour phase (inert gas and/or non-reacted synthesis gas, and/or products of the synthesis reaction in vapour phase under the reaction conditions).
  • the running of the latter can comprise a further two steps: stoppage (or shut down), with consequent re-start-up, and a temporary stoppage phase, better known as stand-by.
  • the inert gas can consist, for example, of nitrogen or, preferably, of purified natural gas.
  • the reactor can be reactivated following the method described above, for example, for the charging phase.
  • the vessel (A) is designed to have a capacity which is such as to contain the volume of suspension present in the reactor (B) and in the other units (E), associated with the treatment of the suspension, at the moment of shut-down.
  • the reactor (B) can be kept in line with the treatment section of the suspension (E) which is completely recycled, ( 11 ) and ( 12 ), to the reactor without the extraction of products.
  • the reactor can be taken off-line from the units (E) after removing the suspension from the equipment (E) directly connected to the reactor (B).
  • the latter is preferably designed to have a capacity which is such as to also contain the volume of suspension present in the units (E) at the moment of temporary stand-by.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Devices And Processes Conducted In The Presence Of Fluids And Solid Particles (AREA)
  • Catalysts (AREA)
  • Supply And Distribution Of Alternating Current (AREA)
US10/572,516 2003-09-18 2004-09-17 Process for the running of a reactor suitable for heterogeneous reactions combined with reactions taking place in three-phase systems Active 2025-01-21 US7550515B2 (en)

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US12/370,682 US7820727B2 (en) 2003-09-18 2009-02-13 Process for the running of a reactor suitable for heterogeneous reactions combined with reactions taking place in three-phase system

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ITM12003A001777 2003-09-18
IT001777A ITMI20031777A1 (it) 2003-09-18 2003-09-18 Procedimento per la gestione di un reattore adatto a reazioni eterogenee in combinazioni con reazioni che si realizzano in sistemi trifasici
PCT/EP2004/010635 WO2005026292A1 (en) 2003-09-18 2004-09-17 Process for the running of a reactor suitable for heterogeneous reactions combined with reactions taking place in three-phase systems

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US (2) US7550515B2 (zh)
EP (2) EP1668093B1 (zh)
CN (3) CN102070385B (zh)
AU (1) AU2004272744B2 (zh)
EA (1) EA009471B1 (zh)
EG (1) EG24325A (zh)
IT (1) ITMI20031777A1 (zh)
NO (2) NO343242B1 (zh)
WO (1) WO2005026292A1 (zh)

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WO2007009954A1 (en) * 2005-07-20 2007-01-25 Shell Internationale Research Maatschappij B.V. Method to start a process for hydrocarbon synthesis
DE102005050526A1 (de) * 2005-10-21 2007-04-26 Choren Industries Gmbh Verfahren zum Haltebetrieb einer Fischer-Tropsch-Synthese
BRPI0619587B1 (pt) * 2005-12-09 2016-05-24 Shell Int Research método para iniciar um processo em estado estacionário para produzir hidrocarbonetos a partir de gás de síntese, e, processo para produzir hidrocarbonetos a partir de uma alimentação hidrocarbonácea
WO2007065904A1 (en) 2005-12-09 2007-06-14 Shell Internationale Research Maatschappij B.V. Method to start a process for producing hydrocarbons from synthesis gas
CN101351528B (zh) * 2005-12-09 2015-11-25 国际壳牌研究有限公司 起动由合成气制备烃的工艺的方法
WO2010069925A1 (en) 2008-12-16 2010-06-24 Shell Internationale Research Maatschappij B.V. High-speed stop in fischer-tropsch process
CN102453498B (zh) * 2010-10-15 2014-05-21 中国石油化工股份有限公司 一种重油悬浮床加氢工艺的停工方法
CN103221513B (zh) 2010-10-27 2015-06-03 沙索技术有限公司 采用随时间失活的催化剂的工艺操作
JP5743643B2 (ja) 2011-03-30 2015-07-01 独立行政法人石油天然ガス・金属鉱物資源機構 反応容器の運転停止方法
FR2984347B1 (fr) 2011-12-14 2015-03-20 IFP Energies Nouvelles Procede de fabrication d'hydrocarbures avec conditionnement du catalyseur
FR2984346B1 (fr) * 2011-12-14 2013-12-27 IFP Energies Nouvelles Procede de fabrication d'hydrocarbures avec chargement en continu du catalyseur
US10329492B1 (en) * 2018-11-13 2019-06-25 Emerging Fuels Technology, Inc. Safe shutdown for a Fischer Tropsch reactor

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PE31698A1 (es) * 1995-11-08 1998-06-15 Shell Int Research Proceso de activacion y rejuvenecimiento de catalizador
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NO20061188L (no) 2006-06-15
EA009471B1 (ru) 2007-12-28
EP1668093B1 (en) 2018-12-05
CN1867648B (zh) 2010-04-28
NO20181196A1 (no) 2006-06-15
EA200600412A1 (ru) 2006-08-25
EP3467075A1 (en) 2019-04-10
EG24325A (en) 2009-01-26
CN102070385B (zh) 2013-11-13
US20070135527A1 (en) 2007-06-14
AU2004272744A1 (en) 2005-03-24
AU2004272744B2 (en) 2009-09-10
ITMI20031777A1 (it) 2005-03-19
NO343242B1 (no) 2018-12-17
EP1668093A1 (en) 2006-06-14
US20090197980A1 (en) 2009-08-06
WO2005026292A1 (en) 2005-03-24
CN102071045B (zh) 2014-10-01
US7820727B2 (en) 2010-10-26
CN1867648A (zh) 2006-11-22
NO343849B1 (no) 2019-06-24
CN102070385A (zh) 2011-05-25
CN102071045A (zh) 2011-05-25

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